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By G. Sachs

THE iron-rich iron-nickel alloys have at-tracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are Atomic per cent nickel FIG. I. FIG. 2. FIG, I.-HONDA'S AND MERICA's IRON-NICKEL DIAGRAM, FIG. 2.-MARSH'S IRON-NICKEL CONSTITU-TIONAL DIAGRAM. the base of many alloys with various out-standing properties. The iron-nickel alloys, therefore, have been investigated exten-sively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,1 and will be discussed in some detail in the sec-tions of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis,2 which is not dependent upon

Jan 1, 1940

By J. E. Fox Jr., J. L. Lummus, J. P. Gallus

Fresh water or brine drilling fluids may be kept free of suspended drilled solids by the addition of a water soluble acrylamide-carboxylic acid copolymer at the flowline. Addition of from .01 to 0.2 lblbbl of the polymer solution to drilling fluids containing less than 5 per cent clay solids by weight causes the solids to flocculate and settle rapidly to the bottom of the pits. Solutions of the polymer injected at the pump suction reduce the loss of water to permeable formations without impairing the permeability to oil. The use of drill-itlg fluids clarified with the polymer has resulted in increased drilling rates, extended bit life, and lower drilling fluid costs. INTRODUCTION Field experience and the results of a number of investigations have established that the accumulation of solids in drilling fluid reduces drilling rate.'-' Drilling with water makes possible higher drilling rates than can be achieved with mud but in many areas drilling with water may not be feasible because of the possibility of encountering high formation pressures or by-dratable formations. To combat these conditions, the drilling fluid must possess certain physical properties such as viscosity, density, fluid loss, etc., which require the presence of solids. The current trend in drilling fluid treatment is to maintain as low a percentage of solids as is possible without harmfully affecting the mud properties needed for drilling. Mechanical separating devices such as wet cyclones and decanting-type centrifuges are proving to be an economical means of controlling the percentage of solids and thereby maintaining low solids muds. Also: special muds have been developed for the purpose of retarding the hydration of drilled solids so that they may be more easily removed by shale shakers or settling pits. In some areas, such as West Texas, the characteristics of some formations will permit drilling with water. However, because of the dispersion of drilled solids, it is usually not possible to maintain clear water even with the aid of mechanical separators, or by utilizing large settling pits. For this reason the commonly used term "water drilling" is a misnomer since the water usually contains some solids. Because of the improved drilling rates and other benefits which might be effected, a laboratory and field study was made of the use of flocculating agents for maintaining clear water for drilling. PROCEDURE Laboratory—Solids Settling Two techniques were employed to determine the effectiveness of flocculating agents in settling solids from drilling mud. First, the rate of fall of solids was measured in graduated beakers containing mud treated with various flocculating agents. Natural gum, oil-in-water emulsions prepared with ethoxylated nonyl phenols and diesel oil. and a powdered synthetic acrylamide-carboxylic acid copolymer* (hereinafter referred to as "polymer") were tested as flocculating agents in both fresh water and salt saturated muds containing 4 per cent solids. The polymer was not added in the powder form directly to the muds but was first dissolved in water in a concentration of 3.5 lb/bbl. The polymer solution was then added directly to the mud. The concentration of the flocculating agents, including the polymer, was varied. High rates of fall of the solids indicated high flocculating efficiency. A second technique consisted of measuring the time in minutes required to obtain clear water at the pump suction after addition of the various flocculating agents at the flowline. These tests were made using a model mud circulating system having a total volume of approximately 10 gal. The natural fresh water and brine muds used contained 4 per cent solids. A sketch of the circulating system appears in Fig. 1. The circulating rate

The problem of surface support in coal mining is naturally divided into three branches: 1. Surface covered with improvements of such value as compared with the value of the underlying coal, or with such elements of danger to mining, that absolute support is essential. 2. Surface with improvements of less value than the underlying coal such that moderate settlement may be permitted, but destructive settlement must be avoided, either by reason of danger to human life or unwarranted property damage. 3. Surface of relatively small value as compared with the underlying coal where destructive settlement may be permitted. First Problem In the first case it is evident that the original support must be maintained either (a) by leaving ample pillars and confining the coal recovery to a very conservative first mining, (b) by so supporting less conservative first mining by filling or flushing that the gradual deterioration of the pillars may be prevented and subsidence avoided, or (c) by incompressible support as masonry either as an adjunct to insufficient pillars or in place of the original coal support. a. From tests made by the Scranton Engineers Club, it appears safe to figure on 2000 Ib. per sq, in. as the safe squeezing strength of coal pillars in place, provided that these are, as usual, not higher than their least horizontal dimension; and from this figure the percentage of pillar to be left for various depths may be easily calculated. For safety in this

Jan 1, 1930

By W. B. Jamison

Man's material advance from one level of civilization to the next has involved the development of new, more useful tools and the utilization of energy greater than he alone could produce. These two essentials for material progress have developed at an ever increasing rate in the last century. While the first really successful use of mechanical energy derived from burning fuel was in James Watt's steam engine which pumped water from coal mines in Cornwall about 1770, there was still very little use of mechanical energy in mining by 1900 except for pumping and hoisting. Compressed air, having some of the characteristics of steam and which operated engines not unlike steam engines or steam hammers, powered the first attempts to mine coal with energy greater than human muscle could provide. When direct current-powered traction cars replaced horse-drawn transportation cars on city streets, it was natural that direct current locomotives should begin to replace animal and human power in mine haulage. Slowly, trolley and battery locomotives were developed and introduced. With d-c systems being established for haulage, it was natural that improved cutting machines should be developed and powered by d-c motors. Thus began the years of

Jan 1, 1961

By M. L. Brashears

IN the last 15 years industrial use of ground water has more than doubled, and in 1951 amounted to 5 billion gallons per day. A similar sharp increase in the utilization of ground water for irrigation and public-water supply occurred in the same period. In many areas rapid increase in withdrawal from wells has taken place almost entirely unhampered by regulatory control and with little or no integration of effort. As might be expected, the chief interest in many regions has been maximum production rather than sustained perennial yield. As a result, widespread depletion of underground reservoirs and deterioration of the quality of the water stored in them has taken place in many areas, even though total pumpage in the United States is far below ultimate potential. Of even more concern is the fact that excessive withdrawal has drawn salt water into the reservoirs beneath many heavily populated centers along the Atlantic, Gulf, and Pacific coasts, causing costly abandonment of pumping plants.' Many hydrologists expect that consumption of water will rise rapidly in the near future, and some predict that industrial requirements will more than double in the next decade.2,3 Thus it appears likely that the draft on many already heavily pumped underground reservoirs will be greatly increased and the search for additional sources of usable ground water intensified in years to come. In view of this, industry as a whole will be forced more and more to recognize the potentialities and limitations of ground-water reservoirs and to utilize them more effectively to prevent costly water shortages and disruption of production. Through painful experience, some industries are already well aware of the need for effective water utilization, and have managed individually or through joint effort to check trends threatening to deplete underground reservoirs completely or to impair the quality of the water. Various remedial measures have been used to bring about successful management of local or regional ground-water resources. Of these, replen-ishment of aquifers by recharge wells or basins has played an important role in overcoming some ground water problems. Artificial recharge of underground reservoirs by water spreading has been practiced successfully in the United States for many years. In the West it has become an important method of salvaging flood run-off for irrigation of crops and maintenance of public water-supply reserves, and it is used to some extent in parts of the East. Artificial recharge by means of wells, on the other hand, is a relatively new development. Until recently it was employed in only a few areas, principally along the East coast. For the last few years, in the ever increasing search for additional water supplies, industry has had greater recourse to this method. Utilization of recharge wells to control the temperature and quality of underground water supplies is also being considered seriously. Operation of recharge wells, like water spreading, is governed largely by local conditions. It requires water relatively low in turbidity, whereas in some areas water spreading has been used successfully with water of high turbidity and silt content. However, water spreading must be employed in large areas and can be carried on effectively only where aquifers crop out at the surface. Recharge wells can be used in limited space. Recharge wells are similar to production wells except that the water flows in the opposite direction. Thus any water-bearing bed that will yield water to wells may be recharged by wells. Often, however, the water available for recharge is of a different character and temperature from that existing in the ground-water reservoir and if transmitted directly underground from a recharge well to a production well might require expensive or difficult treatment before it could be used. Fortunately the physical characteristics of reservoir beds, which control the movement and behavior of ground water, are generally not homogeneous. Moreover, the movement of ground water is very slow because of the frictional resistance of the reservoir beds. By taking full advantage of hydrologic and geologic conditions, it is therefore possible in many instances to bring about favorable changes of temperature and dilution as the water moves from the recharge wells underground to the production wells. Furthermore, if the natural quality or temperature of ground water is unfavorable for industrial purposes, recharge wells may be used to introduce water of more favorable quality or temperature into the ground-water reservoir. When water is discharged into a recharge well, the head in the well is increased. Because of this, a cone of elevation is produced on the water table or the artesian pressure surface in the area surrounding the well. The cone of elevation is similar to the cone of depression produced around a pumping well except that the apex of the cone is above the water table or artesian pressure surface. Thus if a recharge well and a production well tapping the same water-bearing bed are close together, as would be the case at many industrial plants, some of the water discharged from the recharge well would be drawn into the production well within a short time. Under such conditions it is apparent that water of unfavorable temperature and chemical characteristics should not be used for recharging. The more important ground-water reservoirs in the United States often consist of alternating layers of impermeable beds and porous material that will yield water readily to wells. Physical characteristics of individual beds in a ground-water reservoir may not persist over great distances, the impermeable layers grading into beds that will yield large quantities of water. Thus the water-yielding material in underground reservoirs, whether large or small,

Jan 1, 1954

By Francis F. Lucas

A microscope objective of given numerical aperture, when used with light of given wave length, has some fixed limit of resolution. This may be expressed as potential resolving ability—the ability to resolve is inherent in the lens but whether this limit is achieved in practice is quite another matter. Nearly 50 years ago Abbe evolved theoretical considerations which indicated that the ability of a lens to resolve detail is directly proportional to twice the numerical aperture of the objective and inversely proportional to the wave length of the light used. It is true, unquestionably, that as the numerical aperture of the objective is increased the potential resolving ability of the lens is increased and likewise when the wave length of the light used is decreased, the degree of resolution is increased. Whether Abbe's formula expresses the exact relationship is not a matter of great concern. It suffices to know that to improve resolution, other things being equal, two avenues of approach are available. Either the numerical aperture of the objective may be increased or the wave length of the light decreased. With the apochromatic system it is possible to employ successfully wave lengths from 400 to 500 uu and still secure reasonably short exposures. The present limit for numerical aperture is 1.40 N. A. although objectives of 1.60 N. A. are now an experimental possibility for metallurgical work. Thus certain well defined limits are set for those who work within the range of the visible spectrum. In order to take advantage of the increase in resolving power which accompanies a decrease in the wave length of light employed, Dr. A. Kohler and Dr. M. Von Rohr of the Zeiss Scientific Staff developed the "monochromats." These are quartz objectives corrected for the single wave length 275 uu which lies in the ultra-violet region of the spectrum. They also developed a series of quartz oculars and a complete photo-micrographic equipment with which to use the quartz optics. Quartz must be used for the optical parts because glass absorbs ultra-violet light almost completely. Thus there was made available about 20 years

Jan 1, 1926

By Lawrence Adler

In-situ rock has well-recognized rupture and yielding responses. Attention is called to an intermediate response, granulation, which consists of an evenly distributed, small-scale crumbling accompanied by swelling. Granulation results in a negative slope for the inelastic portion of the stress-strain curve as successive interlocks are destroyed, and the load-carrying capacity of the material is reduced. Volumetric swelling with softening also takes place. The prerequisites for such a response are moderate confinement and a uniformly distributed defect pattern. Since rock masses, as well as rock as an intact material, have such patterns in their jointing and texture, respectively, granulation is characteristic of them. The presence of granulation can be demonstrated for a very wide scale, ranging from laboratory testing to regional geologic phenomena. The response of an engineered structure is considered in detail. Granulation appears to be dependent upon internal moments, the formation of which can be controlled by engineering design. The practical implications of such control can be significant in optimizing underground instability and in improving excavation techniques. Rock is usually considered to behave inelastically under high load, by fracturing as a brittle material, or by yielding as a ductile material, ignoring time dependency. These responses, which are characteristic of metallic behavior, appear idealized in Fig. 1, where linear-elasticity approximates the initial behavior. However, another major deformation mechanism peculiar to rock has long been recognized in geology, the granulation of an interlocked material. Granulation consists of a uniformly distributed fracturing and crumbling of the material, accompanied by swelling and softening. Predictably, the associated inelastic portion of the load-deformation curve has a negative slope,

Jan 1, 1971

By F. E. Buch

The smelter is designed for a production capacity of 10,000 short tons of blister copper per month, when operating on the present concentrate grade. The :smelter lay-out is shown in Fig I. The major units of equipment comprise two reverberatory furnaces, three 13 by 30 ft Peirce-Smith converters, two straight line casting machines, one being served by a 13 by 30 ft holding furnace and the other by a ladle tilting quadrant, two converter aisle cranes and two converter blowers. The plant is compact and the general arrangement of standard gauge railway tracks and conveyor belts provides for a smooth flow of incoming materials and metallurgical products. Concentrate is received by conveyor belts and fluxes in standard railway trucks. The local track system is covered by an electric trolley locomotive. The Smelter treats a wet (10 pet moisture) flotation concentrate containing approximately 53 pct total copper and 0.9 pet oxide copper. The predominating minerals are chalco-cite, chalcopyrite and bornite accompanied by small quantities of malachite and cuprite. The gangue is highly siliceous and requires limerock as a flux. Metallurgy would be straightforward were it not for the necessity for eliminating bismuth which occurs as an impurity in the ore along with the copper. Directly or indirectly most of the Smelter problems can be traced to the necessity for bismuth removal. Copper recovery, based on new copper treated, averages 97.5 pct. General Description Flotation concentrate, containing 10 Pet moisture, is conveyed from the filter plant to the smelter storage bins by conveyor belts, the material being weighed in transit by a revolving drum type of weigh-hopper manufactured by Samuel Denison and Son, Ltd. The weigher consists of a steel drum with dished ends carried on a horizontal shaft and rotated by an 8 hp squirrel-cage motor through a worm and Spur reduction gear. A feed mouth in the drum permits of filling and discharging. The whole unit is supported on a framework resting on weighing levers, which in turn connect to transfer levers, thence to an indicator of the steelyard type situated 16 ft from the centre line of the drum. The indicator is of the "Denison" patent equilibrium controlled ticket stamping type, insuring mistake-proof records by a combination of electrical and mechanical movements which Prevent the operator from printing until the cover enclosing the steelyard is closed and until the poise-weights have been Set correctly to the weight of the hopper and contents. The machine is capable of weighing 30 short tons at a time but the usual load is 28 tons. After obtaining the gross weight the drum is rotated and discharged into a receiving bin situated below it. The empty drum is weighed and the net weight re-

Jan 1, 1949

By Francis C. Krauskopf, Carl E. Swartz

Metallurgists differ considerably in their opinions regarding the effect, if any, of small amounts of iron pyrites, or other iron compounds on zinc sulfide ores during the roasting operation. As a result, the literature on this subject expresses many conflicting ideas. The ore, previously crushed to pass through a 1-mm. screen, dries in the roasting kiln, losing water up to 200° to 300° C. At 150° C. iron pyrites begin to lose sulfur. As the temperature increases, while the ore is passing to the hotter part of the furnace, the sulfur burns to sulfur dioxide, leaving the metals as zinc oxide and ferric oxide. These two substances then interact to form zinc ferrite, a compound, yellow brown in color, having the general characteristics of a spinel. Like magnetite, another spinel, zinc ferrite is insoluble in alkalis and dilute acids. As a result, when leached with 10 per cent. sulfuric acid solution, zinc values tied up in this compound remain behind History In the electrolytic recovery of zinc from its ores, the roasted ores are usually leached with a 10 per cent. sulfuric acid solution. When the zinc ore contains iron pyrites as an impurity in an appreciable amount, the actual yield of metallic zinc is much lower than a theoretical calculation would indicate. Further, losses of zinc are, in a rough way, directly proportional to the amount of iron pyrites or other iron compounds present. When the iron is present in the ore in an isomorphous relation to the zinc, as in the case of a marmatite, a greater amount of zinc remains insoluble than when present as a true pyrite or marcasite. Work on the insoluble residues obtained from leaching of the calcines shows that the zinc lost is intimately tied up in this residue. Some investigators have suggested a definite compound, such as zinc ferrite; others merely a mixture of zinc and iron compounds. As early as 1851, Pelouze(')' prepared calcium ferrite by fusion of calcium oxide and ferric oxide. Ebelman, 2) about the same time, prepared

Jan 1, 1928

By G. E. Agar, P. L. De Bruyn

Flotation is an important example of a chemical process by which one solid may be separated from other solids in a mixture. In contrast to other chemical processes such as leaching and smelting, separation of solids by flotation is characterized by the establishment of contact among three phases. In froth flotation these three phases are the solid to be floated, an aqueous electrolyte solution, and a gas, usually air. The gaseous phase may be re- placed by an organic liquid phase or this organic liquid phase may be added deliberately as a fourth phase. To gain an understanding of the flotation sys- tem, it is therefore necessary to study the chemical and physical properties of surfaces and to establish the effect of changes in composition of the bulk phases on the nature of the three interfaces, solid-gas, solid-liquid and liquid- gas. With very few exceptions inorganic solids are completely wetted by the aqueous phase so that the first step in flotation is to replace partially the solid-liquid interface by a solid-gas interface. This displacement process is accomplished by the addition of suitable reagents to the aqueous phase. The resultant surface reaction leaves the solid surface with a hydrophobic film. Although the primary objective of these reagent additions is to alter the solid surface, chemical reactions between the added chemical species and those species derived from the dissolution of the solids are unavoidable. For a quantitative description of such reactions and for the determination of the feasibility of a proposed reaction, we rely on available thermodynamic data. The application of thermodynamic principles to flotation systems has contributed much to our understanding of flotation. The changes in thermodynamic properties such as free energy and chemical potential are accessible to experimental determination, and a knowledge of their magnitude allows us to develop and predict a chemical mechanism oy which a solid becomes floatable. In this chapter it will be assumed that the reader has a working knowledge of the general principles of thermodynamics and solution chemistry. A complete discussion of the physical chemistry of flotation must include a treatment of solubility relations, complex ionic equilibria, reaction potential, and the elements of electrochemistry, especially those dealing with reversible electrical cells. The principles related to all of these features of the flotation system will not be discussed in this chapter. The discussion will be concerned with the thermodynamics and electrochemistry of surfaces and the electrical double layer model of the interface.

Jan 1, 1962

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By F. R. Hensel

PURE silver and silver-lead alloys have been studied as to their suitability for bearings.1-8 A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materials.† The silver-rich end of the diagram as reported in the literature9-11 was found to be sketchy and it was necessary to carry out considerable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. TEST MATERIALS In the beginning of the work, only fused alloys were investigated. Later, research [TABLE I. Composition of Fused Silver thallium Alloys Tested for Antifriction Properties PERCENTAGE ALLOY No.OF THALLIUM 15330.48 153406 231 HT2.04 2312.10 232 HT3.83Balance 2324.07Silver 233 HT5.86 2336.38 2349.84 234 HT10.07] was carried out on electroplating methods and diffusion processes. In preparing the fused alloys, care was taken to exhaust the toxic fumes caused by the thallium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in. diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr2O7, 8 c.c. H2SO4, and 100 c.c. H2O. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C. show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475°C. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not result in complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1945

By Walter R. Hibbard

THE increased strength of a polycrystal-line metallic aggregate compared with that of its individual crystals generally has been associated with complex stress distributions at the grain boundaries resulting from atomic irregularity between grains. This disregistry, together with the necessity for adjacent crystals to deform 'compatibly regardless of the single crystal crystallographic strain mechanism, complicates this mechanism so as to increase the metal's resistance to deformation. Although Taylor1 has shown from purely mechanical considerations the requirement for at least five active slip systems to absorb the complexities during the homogeneous deformation of polycrystalline face-centered cubic metals, experimental studies by Barrett and Levenson2 indicate that this is feasible only in a qualitative sense because of deviations from homogeneous deformation. Seitz and Read in their review3 state: "Unfortunately . . . present knowledge of the grain boundary influence is not sufficient to complement the work in single crystals and provide us with a good foundation for treating polycrystals." The purpose of this investigation was to attempt to clarify the gap between single crystals and crystalline aggregates by an analysis of the effects of deformational stresses. Some of the results were described by C. H. Mathewson in his 1943 Campbell Memorial Lecture.21 PREVIOUS INVESTIGATIONS Since the performance of single crystals deformed under pure stresses has been relatively thoroughly investigated, the most significant researches are concerned primarily with deviations from single crystal behavior of large grained specimens. Qualitative grain boundary effects involving the observed amount of slip were reported by Carpenter and Elam5 in 1921. Individual crystals in a two or three grained aluminum specimen deformed by tension acted in the normal manner described by Taylor and Elam4 except for marked modifications at the grain boundaries. There the power to withstand deformation was considerably increased, leaving a ridge on the specimen where decreased slip occurred, often noticeable 34 in: from the boundary. Adcock,6 Yamaguchi,7 Seumel,8 Hirst9 and others have also reported this phenomenon as a qualitative trend. Yet attempts by O'Neill10 and Ljunggren11 to measure a difference in hardness at grain boundaries in undeformed specimens were unsuccessful. Miller12 measured quantitatively the reduction in slip near the boundary between the single crystal and polycrystalline areas of zinc specimens. These effects consisted of two parts: I. Next to the polycrystalline interface the distribution of stresses was so altered

Jan 1, 1948

By Joseph C. McCaskill

The writer assumes that this volume is not intended to serve as a source of statistics on international trade and that the reader is not interested in wading through a lot of statistical tables copied from the various reporting agencies. Generalizations therefore are made whenever possible and not always is the source of the information meticulously cited. The United Nations regularly publishes trade data on mineral commodities. E. J. Gealy, and C. L Kimbell, of the U S Bureau of Mines (USBM), work with these data and estimate that they cover approximately 78% of total mineral commodities traded. In addition the General Agreement on Tariffs and Trade (GATT) publishes analyses of certain trade data The most complete report of production and trade in minerals 1s probably the international volume of the U.S. Bureau of Mines Yearbook The latest available edition is for 1968, and some of the data in this edition cover only as late as 1967. Unless otherwise stated, the source of data used in the chapter is this Yearbook Other staff members of the Bureau were most helpful and cooperative They are not to be held responsible for conclusions or points of view to be found in the chapter. THE NATURE AND SCOPE OF INTERNATIONAL TRADE The two and a half decades since World War II have witnessed an unprecedented growth international commerce The end of the war found the world economy seriously crippled. Many countries had suffered severe war damage; international trade was disrupted and nations had to resort to exchange controls and bilateral trading arrangements. The postwar recovery, however, was remarkably rapid Within two decades, world Income more than doubled, and world trade which was less than $60 billion in 1948 exceeded $200 billion in 1968, 8 and reached $278 billion in 1970.18 The growing world trade contributed to world prosperity which in turn fostered growth of trade. This dramatic growth of international commerce was made possible by the progressive liberalization of trade and capital movements by the major trading nations of the world which began immediately after the War and has not yet completely lost its steam. The modern-day stimulus of the expanded trade movement was the enactment by the Congress of the United States in 1934, of the

Jan 1, 1976

By Gilbert Santoro

In this study tantalum carbide filaments of various compositions in the fcc region were prepared by heating a tantalum wire in a measured amount of hydrocarbon vapor. Such properties as tensile strength, transverse-rupture strength, microhard-ness, lattice parameter, electrical resistivity, and magnetic susceptibility were measured as a function of carbon content. Some of these properties showed a maximum or a minimum between a carbon-to-tantalum molar ratio of 0.80 and 0.85, the composition range at which the color changes from metallic gray to gold. The recent literature has shown that in the large homogeneity range for the fcc phase of the Ta-C system there is a marked variation for such properties as microhardness,' electrical resistivity, ' thermodynamic properties,z'3 lattice parameter and superconductivity. In addition to the technological interest of these variations within a single phase, important theoretical benefits may ensue from a continuous investigation of properties vs stoichiometry in tantalum carbide and other refractory defect compounds, for example the effect of the metal-metal distance and crystal structure upon bond formation and electronic structure. Whether there is a similar variation of the tensile strength is of practical importance. Of theoretical interest would be the knowledge of how the magnetic susceptibility varies with carbon composition. Both of these properties, as well as the transverse-rupture strength, were determined for tantalum carbide filaments in the fcc phase region. The lattice parameter, the electrical resistivity, and the microhardness were also investigated and compared with values appearing in the literature. EXPERIMENTAL PROCEDURE Material Preparation. Tantalum carbide specimens of various carbon content were prepared by statically carburizing high-purity tantalum filaments in measured quantities of pure hydrocarbon gas. The filaments, which were 10 mil in diameter and 20 or 40 cm long, were heated by their own resistance at temperatures from 1800" to 2200°C using alternating current in some cases and direct current in others. Tantalum wire from two sources was used. One had a reported purity of 99.96 wt pct Ta. The ingot from which this wire was drawn had been electron beam-melted as the final step in its purification. The reported purity of the other wire, which was prepared by a powder metallurgical process, was 99.88 wt pct Ta. The impurities of both tantalum sources are listed in Table I. Spec-trographic-grade toluene or research-grade propane was used as the source of carbon. The apparatus for the carburization of the filaments is shown schematically in Fig. 1. The system was evacuated to 1 x l0-' mm of Hg when using the electron beam-melted tantalum and to less than 1 p when using the less-pure tantalum. Neither the difference in the base vacuum, nor in the hydrocarbon gas, nor in the tantalum filaments resulted in any detectable difference in the properties studied in this work. However, only the carbides prepared from the higher-purity tantalum were used in the magnetic-susceptibility determinations. Once the base vacuum had been reached, the system was flushed with the hydrocarbon and re-evacuated. For any desired composition of the carbide, hydrocarbon gas was allowed to leak into a constant-volume flask to a predetermined pressure. These pressures were measured by a Cartesian diver-type mercury gage with a range from 0 to 20 mm and with a scale expanded to nine times. The hydrocarbon gas was allowed into the reaction tube and the filament was quickly raised to the reaction temperature. The slack in the filament due to thermal expansion was taken up by drawing out the movable electrode with a screw mechanism. The filaments were kept at temperature from a few minutes to 200 hr. In the majority of cases the heating time was 6 hr. The reaction tube was cooled by cascading water on its outer surface. By means of an ammeter and a voltmeter the electrical resistance at the reaction

Jan 1, 1963

By F. George, W. Tice, M. Salkind

It was found that Al-A13Ni could be readily cold rolled perpendicular to but not parallel to the whiskers. Reductions of more than 98 pct were achieved without cracking by rolling perpendicular to the whiskers, whereas extensive edge cracking was noted after only 15 pct reduction when rolling parallel to the whiskers. The longitudinal and transverse tensile strengths were nearly doubled, and the longitudinal yield strength more than tripled by cold rolling 50 pct in a direction perpendicular to the whiskers. The whiskers exhibited some waviness (elastic bending) as a result of cold rolling, but at very high reductions (greater than 75 pct) whisker fracture and misalignment became significant. A fine dislocation substructure in the matrix consisting of cells attached to the whiskers was pro -duced by cold rolling. Most of- the substructure was readily removed by a 1-hr anneal at 500°C. Cold rolling was found to substantially reduce the thermal stability of the microstructure at 610°C but did not affect the stability at 500°C. FIBER and whisker reinforced composite materials promise significant improvements in properties over conventional materials. Before they find wide use, however, it will be necessary to understand the response of these highly anisotropic materials to common metalworking processes. Most of the nonmetal-lic fiber reinforced materials have very low elongations (a few pct or less) in the direction of fiber alignment. Thus, metalworking techniques such as rolling and forging would not be as broadly applicable to these materials. This investigation was initiated to determine how a composite system consisting of Al3Ni whisker reinforced aluminum responded to rolling, what changes in the microstructure occurred, and the effect of deformation on the mechanical properties. The composite material studied was produced by unidirectional solidification of the A1-Al3Ni eutectic alloy'-7 and consisted of 10 pct by volume of aligned whiskers of Alai in a matrix of aluminum. It should be pointed out that this system is not representative of all composite materials, and the results will therefore not be universally applicable. The A1-Al3Ni system is characterized by: 1) A strong fiber-matrix interfacial bond 2) A ductile matrix 3) A sufficiently low fiber content to allow significant plastic flow between fibers 4) Strong, completely elastic whiskers (tensile strength 400,000 psi, elastic modulus = 20 X 106 psi.1 These factors allow the material to be readily rolled perpendicular to the fibers. If the fiber-matrix bond were not strong, such a weak interface could fail during rolling. A measure of the ability of a composite to be rolled in the transverse direction can be obtained from noting the transverse tensile behavior. In the case of Al-Al3Ni,2 there is considerable ductility (15 to 30 pct). In the case of boron filament reinforced aluminum, for example, the transverse elongation is less than 1 pct,8 and the material could probably not be cold rolled as readily in that direction. EXPERIMENTAL PROCEDURE 3-in. diam ingots of A1-A13Ni eutectic were unidi-rectionally solidified in graphite crucibles. The starting materials consisted of 99.99+ pct pure nickel and aluminum, and the pure eutectic ingots were made with 6.2 wt pct Ni. The unidirectional solidification process (described in detail elsewhere1-3) consists of preparing a master heat of eutectic composition, remelting, and withdrawing the ingot vertically downward through the heat source at a controlled rate so that plane front solidification proceeds upward at a constant velocity. The resulting microstructure consists of 10 pct by volume of whiskers of very high aspect (length to diameter) ratio. The fiber lengths have not been measured because of the difficulty of detecting fiber ends9 but exceeds 104. There is some possibility that the fibers may be continuous within one grain. Flat sheet specimens 2¾ in. sq and approximately 0.2 in. thick containing whiskers parallel to the plane of the sheet and to one edge were used for this study. A1-A13Ni exhibits either a rod-like (high solidification rates) or a blade-like (low solidification rates) whisker morphology,1,3 and both types were studied. Rolling was accomplished using a two-high rolling mill at a speed of approximately 10 fpm. The rolling direction was either parallel to or perpendicular to the direction of growth (direction of whisker alignment). Reductions of from 0.002 to 0.03 in. per pass were used with the most common value being 0.005 in. per pass. Cold rolling of Al-Al3Ni to more than 98 pct reduction in thickness was accomplished with no intermediate anneals. In addition. a series of speci-mens was cold rolled 97 pct with a 1-hr, 500°C anneal in air after each 50 pet reduction. Tensile testing was accomplished using a Tinius-lsen four screw testing machine. Flat sheet specimens + in. wide and between 2 and 2; in. long with the thickness dependent upon rolling reduction, were used. The gage section was in. wide and 1 in. long. Strain was measured using a clip-on LVDT extensome-

Jan 1, 1970

By M. L. Fuller

DURING the last several years many papers have appeared dealing with the structure of highly polished metal surfaces. The awakening of interest in this subject is due to the applicability of the electron diffrac-tion technique to the study of surfaces. The original theory of Beilby1 considered the surface of polished metals as of the nature of a super-cooled liquid or a vitreous, amorphous solid. The electron diffraction effects from polished metals have been interpreted by many to be a direct experimental proof of the correctness of the Beilby theory. This inter-pretation has been strongly opposed by others, so that at the present time the subject is in an uncertain and controversial state. In the present paper new, and hitherto unpublished, electron diffrac-tion effects from polished zinc are described. These observations indicate that the polished surface of zinc is crystalline.

Jan 1, 1938

By R. Wiesenthal

A method is developed for improving the low recovery efficiency which results when viscous oils are flooded by water. Viscous oil has been diluted with a lighter liquid miscible in it in any ratio which produces a mixture possessing a reduced viscosity and which is then displaced by water. Light gasoline was used in these tests to reduce the viscosity of the oil in place. Oils possessing viscosities in the range of 1.28 to 324 cp at the test temperature of 30C were displaced from a cylindrical unconsolidated sand core, with a length of 2 m (6.6 ft) and a diameter of 10 cm (3.9 in.) at a flood of 6.27 cc/sq cm/hr. In two test series up to I PV of light gasoline was injected into the core before water flooding. In the first series the recovery of a low-viscosity oil (1.28 cp) increased as the volume of light gasoline was increased. However, only the oil which could not be recovered by water flooding alone could be replaced by the light gasoline. In the other series, the recovery of a more viscous oil (13.5 cp) was not increased even if large quantities of light gasoline were injected. An oil bank built up ahead of the water front so that the flood water met with equivalent saturation conditions, as would be the case in flooding solely with water. However, the recovery of more viscous oils could be increased substantially when the core was first flooded with water, followed by a slug of light gasoline, and then flooded with water again. Furthermore, an oil bank ,built up ahead of the second water front. The formation of this oil bank is particularly favorable for the displacement process; the greater part of the light gasoline injected was pushed out of the core ahead of the oil and recovered. Using a light oil of low viscosity, it was possible to replace only the residual oil that could not be recovered by water flooding by the light gasoline. As the basic study had shown that highly viscous oils could be recovered by flooding first with water, then with light gasoline, followed by a second injection of water, the study was extended by tests made with reservoir fluids and cores taken from the low-gravity oil reservoir of the Wietze field, Germany. A great increase in recovery over flooding with water alone was obtained in these tests. The results may show a way to recover high-viscosity oils by a comparatively simple flooding procedure. INTRODUCTION In fields where oil recovery has not benefited from natural water drive, increased recovery may be obtained by the injection of water into the reservoir, especially in the case of fields which produce high-gravity, low-viscosity oil. There is a rather close relation between the viscosity of the reservoir fluid and the recovery that can be obtained by water flooding. As the viscosity increases the oil recovery decreases proportionately, so that an oil viscosity about 30 times that of water is generally considered to be the upper limit for an economically successful water flood.' This limitation has been recognized theoretically by Buckley and Leverett,' and has been verified by numerous laboratory flooding tests, such as by Croes and Schwarz,V n the viscosity ratio range of oil to water from 1 to 500. The reason for the inferior recovery of viscous oils by water flooding can best be understood by considering the mechanism of flood tests. In such tests water is introduced into one end of a sand-packed tube which is saturated with oil of the viscosity to be tested, and oil is produced from, the other end. Oil, with a viscosity lower than that of water, is pushed ahead of the advancing water with considerable uniformity, and irregularities in the displacement process tend to be eliminated as the oil saturation decreases and the water saturation increases. However, oil recovery is not complete, for the water forms interfaces with the oil and traps residual oil droplets in certain of the pore spaces. These residual oil droplets are distributed rather uniformly through the sand, and they are not susceptible to recovery regardless of the amount of water passed through the test cylinder. In the case of an oil possessing a viscosity greater than that of water, the injected water tends to move irregularly through the sand in the test cylinder. At the place in the sand where initial water movement takes place, resistance to the movement of water is lowered and the water finger so formed will grow perceptibly; it will extend to the outlet end of the test cylinder so that a breakthrough of water takes place long before much of the oil-saturated volume of the sand has come in contact with water. Once the breakthrough of water takes place, the water-oil ratio is gradually approaching the economic limit, even though much of the oil in the test cylinder remains unaffected by water. Disconnected drops of oil are trapped in the portion of the sand that has been invaded by water, just as when an oil of low viscosity is flooded. The poor recovery of the more viscous oils, therefore, is due to the irregularity of water movement through the test cylinder, and the rate of water movement through restricted sections of the oil-saturated sand increases with the more viscous oils. There are three ways whereby the recovery of viscous oils by water flooding can be improved:' (1) adding materials which will increase the vis-

Jan 1, 1965

By G. Van Esbroeck, M. Van Weyenbergh

The copper mines of the Katanga region in the Belgian Congo lie along the same mineralized belt as those of Northern Rhodesia. There are two distinct types of deposits in that belt, the dolomitic and the quartzitic. In the dolomitic type the metallic minerals are found in a dolomitic limestone country rock. Through oxidation and enrichment, large deposits of high-grade oxidized copper ores were formed, some of which are being worked by the Union Minière du Haut Katanga. Such deposits are all in Katanga. The quartzitic deposits are found in Katanga and Northern Rhodesia. Here the primary mineralization occurred in sandstones and quartzites, in horizons stratigraphically lower than the dolomites. These rocks are not favorable to secondary enrichment and the oxidized zone is poorer than the sulphide zone, which alone contains the ore. There are also in Katanga a few ore-bearing veins. One of them is being worked in the Prince Leopold mine at Kipushi. Prince Leopold Mine The Kipushi ore body fills a fault vein and invades the wall rocks more or less extensively by metasomatic replacement. The vein strikes north-northeast and south-southwest and dips to the west. The variable dip averages 60' to a depth of 300 ft., and more uniformly 80' below 400 ft. In the upper section the average width is 200 ft. and below the width is about 150 ft. The length of the ore body is 2300 feet. The eastern side of the vein—the footwall—is dolomitic and contains irregular masses of ore sometimes extending 100 ft. or more from the main

Jan 1, 1940

By M. Van Weyenbergh, G. Van Esbroeck

The copper mines of the Katanga region in the Belgian Congo lie along the same mineralized belt as those of Northern Rhodesia. There are two distinct types of deposits in that belt, the dolomitic and the quartzitic. In the dolomitic type the metallic minerals are found in a dolomitic limestone country rock. Through oxidation and enrichment, large deposits of high-grade oxidized copper ores were formed, some of which are being worked by the Union Minière du Haut Katanga. Such deposits are all in Katanga. The quartzitic deposits are found in Katanga and Northern Rhodesia. Here the primary mineralization occurred in sandstones and quartzites, in horizons stratigraphically lower than the dolomites. These rocks are not favorable to secondary enrichment and the oxidized zone is poorer than the sulphide zone, which alone contains the ore. There are also in Katanga a few ore-bearing veins. One of them is being worked in the Prince Leopold mine at Kipushi. Prince Leopold Mine The Kipushi ore body fills a fault vein and invades the wall rocks more or less extensively by metasomatic replacement. The vein strikes north-northeast and south-southwest and dips to the west. The variable dip averages 60' to a depth of 300 ft., and more uniformly 80' below 400 ft. In the upper section the average width is 200 ft. and below the width is about 150 ft. The length of the ore body is 2300 feet. The eastern side of the vein—the footwall—is dolomitic and contains irregular masses of ore sometimes extending 100 ft. or more from the main

Jan 1, 1940